Methods of combatting insects,fungi or nematodes using phosphono thioester amidates

ABSTRACT

COMPOUNDS ARE PREPARED HAVING THE FORMULA   R1-S-P(=X)(-R2)-R3   WHERE R1 IS TRICHLOROETHYL OR DICHLOROVINYL, R2 IS LOWER ALKYL OR PHENYL, R3 IS OR4 OR SR4 OR   -N(-R5)-R6   WHERE R4 IS ALKYL, ARYL, HALOALKYL OR HALOARYL, R5 AND X IS O OR S. PREFERABLY R4 AND R5 ARE LOWER ALKYL AND R6 IS H OR LOWER ALKYL. THE COMPOUNDS ARE USEFUL AS NEMATOCIDES, FUNGICIDES, AND INSECTICIDES. PREFERABLY R1 IS 2,2,2,TRICHLOROETHYL OR 2,2-DICHLOROVINYL.

United States Patcnt O METHODS OF COMBATIING INSECTS, FUNGI R NEMATODESUSING PHOSPHONO THIOESTER AMIDATES Paul C. Aichenegg, Prairie Village,Kans., assignor to Chemagro Corporation, Kansas City, Mo. H

No Drawing. Application Dec. 31, 1969, Ser. No. 889,688, which is acontinuation-in-part of application Ser. No. 620,664, Mar. 6, 1967, nowPatent No. 3,489,825, dated Jan. 13, 1970. Divided and this applicationlNov. 5, 1971, Ser. No. 196,183

Int. Cl. A0111 9/36 US. Cl. 424-220 9 Claims ABSTRACT OF THE DISCLOSURECompounds are prepared having the formula where R is trichloroethyl ordichlorovinyl, R is lower alkyl or phenyl, R is CR or SR, or

where R, is alkyl, aryl, haloalkyl or haloaryl, R and X is 0 or S.Preferably R and R are lower alkyl and R is H or lower alkyl. Thecompounds are useful as nematocides, fungicides, and insecticides.Preferably R is 2,2,2- trichloroethyl or 2,2-dichlorovinyl.

This is a division of application Ser. No. 889,688 filed Dec. 31, 1969which is a continuation-in-part of application Ser. No. 620,664, filedMar. 6, 1967, and now Pat. No. 3,489,825 of Jan. 13, 1970. The entiredisclosure of the parent application is hereby incorporated byreference.

The present invention relates to the preparation of novel phosphonatesthiophosphonates, phosphonamidates and thiophosphonamidates.

It is an object of the present invention to prepare novel phosphonates,thiophosphonates, phosphonamidates and thiophosphonamidates.

Another object is to kill nematodes.

An additional object is to kill fungi.

A further object is to kill insects.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by preparingcompounds having the formula II as P-R,

where R is trichloroethyl or dichlorovinyl, R is lower alkyl or phenyl,R is OR., or SR, or

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where R, is alkyl, aryl, haloalkyl or haloaryl, R is alkyl, aryl orhaloaryl and R is hydrogen or R and X is O or S. Preferably R and R arelower alkyl, e.g. l-8 carbon atoms and most preferably not over 4 carbonatoms, and R is H or lower alkyl (as for R and R If a halogen is presenton R R or R it is preferably chlorine but can be bromine or fluorine.Preferably R is 2,2,2-trichloroethyl or 2,2-dichlorovinyl.

The compounds of the invention are useful as nematocides, fungicides andinsecticides. The activity of the compounds for the several uses variesto a considerable extent depending upon both the compound and its in--tended use. Because of their relatively low phytotoxicity, they are veryuseful as agricultural pesticides.

The compounds of the present invention are conveniently prepared by thefollowing reaction:

The compounds of Formula I include S-2,2,2-trich1oroethyl methylphosphonyl chloride (GP 12), S-2,2,2-trichloroethyl ethyl phosphonylchloride (CP 22), S-2,2,2- trichloroethyl propyl phosphonyl chloride,S-2,2,2-trichloroethyl butyl phosphonyl chloride, S-2,2,2-trichloroethylisobutyl phosphonyl chloride, S 1,2,2 trichloroethyl methyl phosphonylchloride, S-1,2,2-trichloroethyl ethyl phosphonyl chloride,S-2,2,2-trichloroethyl phenyl phosphonyl chloride (CP 8),S-l,2,2-trichloroethy1 phenyl phosphonyl chloride, S-2,2-dichlorovinylmethyl phosphonyl chloride (CP 14), S-2,Z-dichlorovinyl ethyl phosphonylchloride (CP 23), S 2,2-dichlorovinyl propyl phosphonyl chloride,S-2,2-dichlorovinyl isopropyl phosphonyl chloride, S-2,2-dichlorovinylbutyl phosphonyl chloride, S-2,2-dichlorovinyl phenyl phosphonylchloride (CP 10), S-2,2,2-trichloroethyl methyl thiophosphonyl chloride(GP 16), S-2,2,2-trichloroethyl ethyl thiophosphonyl chloride (CP 32),S-2,2,2-trichloroethyl propyl thiophosphonyl chloride,S-2,2,2-trichloroethyl butyl thiophosphonyl chloride,S-2,2,2-trichloroethyl phenyl thiophosphonyl chloride (CP 9),S-1,2,2-trichloroethyl methyl thiophosphonyl chloride,S-1,2,2-trichloroethyl ethyl thiophosphonyl chloride,S-1,2,2-trichloroethyl thiophosphonyl chloride, S-2,2-dichlorovinylmethyl thiophosphonyl chloride (CP 15), S-2,2-dichlorovinyl ethylthiophosphonyl chloride (CP 33), S -2,2-dichlorovinyl propylthiophosphonyl chloride, S-2,2-dichlorovinyl butyl thiophosphonylchloride, S-2,2-dichlorovinyl phenyl thiophosphonyl chloride (CP 11).

As compounds of Formula II for reaction with compounds of Formula Ithere can be used alcohols such as methyl alcohol, ethyl alcohol, propylalcohol, isopropyl alcohol, butyl alcohol, octyl alcohol, sec. octylalcohol, isooctyl alcohol, amyl alcohol, 2,2,2-trichloroethyl alcohol,ethylene chlorohydrin, propylene chlorohydrin, trimethylenechlorohydrin, 1,2-dichloro-2-propanol, ethylene bromohydrin, allylalcohol, or phenols (preferably in the form of their sodium salts), e.g.phenol per se, p-cresol, m-cresol, o-cresol, p-ethyl phenol,2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, p-t-butyl phenol,p-octylphenol, 2-methyl-4-chlorophenol, 2,4,5-trichlorophenol,pbutylphenol, or mercaptans, e.g. methyl mercaptan, isopropyl mercaptan,ethyl mercaptan, propyl mercaptan, butyl mercaptan, sec. butylmercaptan, thiophenol, p-tbutyl thiophenol, amyl mercaptan, octylmercaptan, 2,4,5- trichlorothiophenol, 2-methyl-4-chlorothiophenol; orprimary or secondary amines, e.g., methyl amine, ethyl amine, isopropylamine, propyl amine, butyl amine, isobutyl amine, amyl amine, hexylamine, cyclohexyl amine, piperidine, pyrrolidine, octyl amine, dimethylamine, di-

ethyl amine, dipropyl amine, dibutyl amine, diamyl amine, diisopropylamine, aziridine (ethylene imine), dioctyl amine, diisobutyl amine,aniline, N-methylaniline, N-ethyl aniline, m-chloro aniline, a-naphthylamine, B- naphthyl amine, pbromoaniline, N-butyl aniline, otoluidine,p-toluidine, p-chloroaniline, O-chloroaniline.

Examples of compounds within the present invention areS-2,2,2-trichloroethyl O-butyl methyl phosphonate,S-'2,2,2-trichloroethyl-O-butyl thiophosphonate, S-2,2,2 trichloroethylO-amyl ethyl phosphonate, S-2,2,2-trichloroethyl-O-amyl thiophosphonate,S-2,2,2-trichloroethyl O-octyl methyl phosphonate,S-2,2,2-trichloroethyl O-octyl ethyl thiophosphonate,S-2,2,2-trichloroethyl O- butyl butyl phosphonate,S-2,2,2-trichloroethyl O-hexyl butyl thiophosphonate, S,SdichlorovinylO-butyl methyl phosphonate, S,S-dichlorovinyl O-octyl ethylthiophosphonate, S-1,2,2-trichloroethyl O-ethyl methyl phosphonate,S1,2,2-trichloroethyl O-methyl ethyl thiophosphonate,S-2,2,2-trichloroethyl O-2-chloroethyl methyl thiophosphonate,S-2,2,2-trichloroethyl O-Z-bromoethyl ethyl ethyl phosphonate,S-2,2,2-trichloroethyl-O-phenyl methyl phosphonate,S-2,2,2-trichloroethyl-O-phenyl ethyl thiophosphonate,S-2,2-dichlorovinyl-O-phenyl ethyl phosphonate,S-2,2-dichlorovinyl-O-phenyl methyl thiophosphonate,S-2,2-dichlorovinyl-O-phenyl phenyl phosphonate,S-2,2,2-trich1oroethyl-O-p-cresyl methyl phosphohate,S-2,2,2-trichloroethyl O-m-cresyl ethyl thiophosphonate,S-2,2-dichlorovinyl O-o-cresyl ethyl thiophosphonate,S-2,2,2-trichloroethyl-S-methyl methyl phosphonate,S-2,2,2-trichloroethyl-S-ethyl methyl thiophosphonate,S-Z,2-dichlorovinyl-S-butyl ethyl phosphonate, S-2,2-dichlorovinyl-S-octyl methyl thiophosphonate, S-2,2,2-trichloroethyl-S-phenyl ethyl phosphonate, S-2,2,2-trichloroethylmethyl phosphon mono octyl amidate, S-2,2, 2-trich1oroethyl ethylphosphon dioctyl amidate, S-2,2-dichlorovinyl methyl phosphon mono butylamidate, S- 2,2,2-trichloroethyl ethyl thiophosphon diheptyl amidate,S-2,2-dichlorovinyl methyl thiophosphon mono butyl amidate,S-2,2,2-trichloroethyl ethyl phosphon mono phenyl amidate,S-2,2-dichlorovinyl methyl phosphon mono alpha naphthyl amidate,S-2,2,2-trichloroethyl methyl thiophosphon diphenyl amidate,S-2,2-dichlorovinyl ethyl phosphon p-chlorophenyl amidate. Additionalcompounds within the invention are set forth in the working examples.

In the working examples the compounds of Formula I are indicated by theappropriate CP numbers as set forth supra.

Unless otherwise indicated, all parts and percentages are by weight.

Specific examples of the preparation of such derivatives are set forthbelow.

EXAMPLE 1 6.1 grams (0.023 mole) of CP 12 were dissolved in 60 ml. ofSkellysolve B-benzene (1:5 by volume). 38 grams (0.023 mole) of2,4-dichlorophenol in ml. of benzene were added and the reaction waseffected by dropwise addition of 2.3 grams (0.023 mole) of triethylaminein 10 ml. of Skellysolve B with stirring and cooling at a temperaturenot to exceed C. 1.5 hours warming at 50 C., cooling, washing insuccession with dilute hydrochloric acid, dilute aqueous sodiumbicarbonate and water, drying over anhydrous magnesium sulfate and highvacuum stripping gave 8.8 grams (98% yield) of crudeS-2,2,2-trichloroethyl-O 2,4-dichlorophenyl methyl phosphonate (Compound6702) as a buff colored solid which after a short wash with SkellysolveB gave white crystals, M.P. 86 C.; Cl, 44.7% (Theory 45.6%); S, 8.3%(Theory 8.25%); P, 7.9% (Theory 7.9%).

Skellysolve B is an aliphatic hydrocarbon solvent boiling in the hexanerange.

EXAMPLE 2 11.05 grams (0.04 mole) of CP 22 were diluted with 100 ml. ofdry chloroform and 4.2 grams (0.08 mole) of monoisopropyl amine in 10ml. of chloroform were added dropwise with stirring and cooling at 5l0'C. After completed addition the whole mixture was allowed to stir atroom temperature overnight. Washing with dilute HCl, dilute NaHCO andwater, drying over anhydrous MgSO and stripping off of the chloroformgave 11.5 grams (96.5% yield) of S-2,2,2-trichloroethyl ethylphosphon-monoisopropyl amidate (Compound 7835) as a light amber viscousoil, 11 1.5213.

EXAMPLE 3 9.7 grams (0.03 mole) of CP 8 in 10 ml. of Skellysolve B wereadded to 3 grams (i.e. a large excess) of ethyl mercaptan in 50 m1. ofSkellysolve B. 3.0 grams of triethylamine (0.03 mole) in 10 ml. ofSkellysolve B were then added dropwise with stirring at below 35 C. overa. period of 20 minutes. Stirring at room temperature for 2 furtherhours, Washing the mixture with dilute HCl, dilute NaHCO and water,drying of the, organic layer over MgSO, and stripping gave 10.0 gramsyield) of S-2,2,2-trichlor0ethyl-S-ethyl phosphonate (Compound 6645) asan almost colorless and odorless viscous oil, r1 1.5992; Cl 30.2%(Theory 30.5%), P 8.7% (Theory 8.9%

EXAMPLE 4 11.1 grams (0.04 mole) of CP 16 were dissolved in ml. ofchloroform and 4.8 grams (0.08 mole) of monoisopropyl amine in 10 ml. ofchloroform were added dropwise with stirring at 510 C. with cooling. Themixture was allowed to Warm to room temperature and stand overnight.Washing of the chloroform solution with dilute HCl, dilute NaHCO andwater, drying over anhydrous MgSO and stripping of the organic solutionsgave 11.5 grams (96% yield) of S-2,2,2-trichloroethyl methylthiophosphon-monoisopropyl amidate (Compound 7836) as an almostcolorless, very viscous oil, n 1.5747.

EXAMPLE 5 11.7 grams (0.04 mole) of CP 32 were dissolved in 100 ml. ofchloroform and a solution of 4.8 grams of monoisopropyl amine in 10 ml.of chloroform was added dropwise with stirring at 5-10 C. withoccasional cooling. Additional slow stirring overnight at roomtemperature, washing of the resulting mixture in succession with diluteHCl, dilute NaHCO and water, drying over anhydrous magnesium sulfate andstripping gave a 90% yield of S-2,2,2-trichloroethyl ethyl thiophosphonmonoisopropyl amidate as a viscous, colorless oil, 11 1.5684 (Compound7837).

EXAMPLE 6 10.2 grams of CP 9 (0.03 mole) were diluted with 50 ml. ofbenzene and 2 grams (a slight excess) of ethyl alcohol were added. 3grams (0.03 mole) of triethyl amine in 10 ml. of benzene were added withstirring and cooling at room temperature in order to complete thereaction. Standing overnight and working up by washing with dilute HCl,dilute Na'HCO and water, drying over MgSO and high vacuum stripping gave9.7 grams (93% yield) of S2,2,2-trichloroethyl -O- ethyl phenylthiophosphonate (Compound 7823) as a yellow oil, n 1.6030.

EXAMPLE 7 13.55 grams (0.06 mole) of CP 14 dissolved in 100 ml. ofpetroleum ether were reacted with 7.2 grams (0.12 mole) of monoisopropylamine at room temperature. (The temperature did not exceed 30 C.) 50 ml.of henzene were added to make the product soluble in the organic layer.Washing with dilute HCl, dilute NaHCOg and water, drying over MgSO andstripping gave 10 grams (67% yield) of S-2,2-dichlorovinyl methylphosphon monoisopropyl amidate (Compound 7587) as an amber, viscous oil,n 1.5486.

EXAMPLE 8 To grams (0.042 mole) of CP 23 in 50 ml. of dry chloroformthere were added 3 grams (0.042 mole+0.5 gram excess) of ethyl mercaptanat 0-5 C. followed by dropwise addition of 4.25 grams (0.042 mole) oftriethylamine in 20 ml. of chloroform with cooling and stirring.Stirring at room temperature for 3 hours, washing with dilute HCl,dilute NaHCO and water and drying over MgSO gave after high vacuumstripping 9.9 grams (89% yield) of S-2,2-dichlorovinyl S-ethylphosphonate (Compound 7502) as a light viscous oil, n 1.5756.

EXAMPLE 9 To 8.61 grams (0.03 mole) of CP 10 in 100 ml. of petroleumether stirred and cooled to 1015 C. there were added 3.0 grams (about a10% excess) of dimethylamine at a moderate rate at a temperature of notover C. Finally the whole mixture was stirred for 30 minutes at roomtemperature. Addition of 50 ml. of henzene to dissolve all of theproduct formed, washing with dilute HCl, dilute NaHCO and water, dryingo-ver MgSO and stripping of the organic layer gave 7.5 grams (85% yield)of S-2,2-dichlorovinyl phenyl phosphono N,N-dimethyl amidate (Compound6707) as a brown oil, 12 1.5942.

EXAMPLE 10 To 9.5 grams (0.039 mole) of CP 15 in 100 ml. of chloroformthere were added with stirring and cooling at 15-20 C. a solution of4.64 grams of monoisopropyl amine in 10 ml. of chloroform. Stirring atroom temperature for 2 more hours, washing with dilute HCl, dilute NaHCOand Water, drying over anhydrous MgSO and high vacuum stripping gave 9.8grams (94% yield) of S-2,2-dichlorovinyl methylthiophosphon-N-monoisopropyl amidate (Compound 7590) as an amber oil,11, 1.5882, Cl 27.2% (Theory 26.8%), P 11.4% (Theory 11.7%), S 23.3%(Theory 24.2%).

EXAMPLE 11 9.5 grams (0.037 mole) of CP 33 in 100 ml. of chloroform wasreacted with 4.4 grams of monoisopropyl amine (an excess) in 10 ml. ofchloroform by dropwise addition of the amine solution with stirring at5-10 C. with cooling. The mixture was warmed for 30 further minutes at4550 C. Washing when cooled to room temperature with dilute HCl, diluteNaHCOg and water, drying over MgSO and high vacuum stripping gave 10grams (97% yield) of S-2,2-dichlorovinyl ethylthiophosphon-N-monoisopropyl amidate (Compound 7592) as an amber oil, 111.5807.

EXAMPLE 12 To 12 grams (0.039 mole) of CP 11 in 100 ml. of carbontetrachloride there were added 3 grams (an excess) of ethyl mercaptanfollowed by dropwise addition with stirring and cooling of 4 grams (thecalculated amount) of triethylamine at 25-30 C. Further stirring at roomtemperature overnight, Washing with dilute HCl, dilute NaHCO and water,drying over MgSO and stripping gave 11 grams (85% yield) ofS-2,2-dichlorovinyl S ethyl phenyl thiophosphonate (Compound 7830) as alight yellow oil, 11 1.6634.

EXAMPLE 13 10 grams (0.382 mole) of CP 12 were diluted with 75 ml. ofbenzene and 2.5 grams (0.4 mole, slight excess) of ethyl mercaptan wereadded at room temperature followed by dropwise addition with stirring of3.9 grams (0.28 moles) of triethylamine at such a rate (occasionalcooling) that the temperature was continued for 2.5 hours and the wholewas allowed to stand overnight with stirring. Filtration, washing of theclear benzene solution with dilute HCl and dilute bicarbonate, dryingover magnesium sulfate and high vacuum stripping gave 95 grams (87%yield) of S-2,2,2-trichloroethyl-S-ethyl-methylphosphonate as lightyellow oil, 11 1.5621.

EXAMPLE 14 10 grams (0.38 mole) of CP 12 were diluted with ml. ofbenzene, 1.9 grams ethanol (0.4 mole, slight excess) added at once atroom temperature followed by dropwise addition with stirring of 3.9grams (0.38 mole) of triethylamine at a temperature not to exceed 25 C.Standing overnight at room temperature and washing as described inExample 13 followed by high vacuum stripping gave 9 grams (87% yield) ofS-2,2,2-trichloroethyl- O-ethyl-methylphosphonate as reddish oil, 111.5148.

EXAMPLE 15 10.5 grams (0.4 mole) of CP 12 were diluted with ml. ofchloroform and reacted with a total of 4.8 grams (0.8 mole) ofisopropylamine by dropwise addition with stirring and cooling at atemperature of between 10 and 20 C. After completed addition of thereagent the mixture was allowed to stir for a further /2 hour at roomtemperature followed by standing overnight. After a brief warming periodto 50 C. next day (15 minutes) and cooling, the mixture was Washed insuccession with water, dilute HCl and dilute bicarbonate, dried overanhydrous magnesium sulfate and stripped in high vacuum. 11 grams (97%yield) of compoundS-2,2,2-trichloroethyl-methylphosphon-monoisopropylamidate were thusobtained as reddish oil, n 1.5196.

EXAMPLE l6 8 grams (0.3 mole) of CP 12 were diluted with 1 ml. ofbenzene at room temperature and 7.1 grams (0.7 mole) di-isopropylaminewere added dropwise with stirring allowing the temperature to rise to 35C. Stirring was continued at room temperature. for approximately 3 hoursand the whole was allowed to stand overnight at room temperature. Thefollowing day the mixture was washed in succession with dilute HCl,dilute bicarbonate, dried over anhydrous magnesium sulfate, and highvacuumed stripped. 1.5 grams (12.8% yield) ofS-2,2,2-trichloroethyl-methylphosphon N,N di-isopropylamidate wereobtained as brownish oil, 11 1.5432.

EXAMPLE 17 10 grams (0.445 mole) of CP 14 were diluted with 100 ml. ofbenzene and 2.3 grams (0.5 mole) of dry ethyl alcohol added at roomtemperature. To this solution there were added slowly with stirring andoccasional cooling 4.5 grams (0.0445 mole) of triethylamine dropwisewith stirring at such a rate that the temperature did not exceed 25 C.After completed addition of the reagent, stirring was continued for afurther 2 /2 hours and the whole was allowed to stand overnight at roomtemperature. Washing the mixture with dilute HCl, dilute bicarbonate,drying the solution over anhydrous magnesium sulfate and high vacuumstripping gave 9 grams (86% yield) ofS-2,2-dichlorovinyl-O-ethyl-methylphosphonate as amber oil.

EXAMPLE 18 13.55 grams (0.6 mole) of CP 14 were diluted with 100 ml. ofdry chloroform and 3.72 grams (slight excess) of ethyl mercaptan wereadded at room temperature at once. 6.06 grams (0.6 mole) oftriethylamine were then added dropwise with stirring and cooling at arate that the tem-- perature remained below 25 C. Allowing the mixtureto stand overnight, washing with dilute HCl, sodium bicarbonate, dryinganhydrous magnesium sulfate and high vacuum stripping gave 12.4 grams(83% yield) of S2, 2-dichlorovinyl-S-ethyl-methylphosphonate as almostcolorless oil, 11 1.5616.

EXAMPLE 19 10 grams (0.445 mole) of CP 14 were diluted with 100 ml. ofbenzene and 10.1 grams (0.1 mole) of dilute isopropylamine were addeddropwise with stirring and cool- EXAMPLE 20 grams (0.036 mole) of CP 16were diluted with 75 ml. of dry benzene and 1.48 grams (0.04 mole) ofdry ethanol were added at room temperature. 3.64 grams of triethylamine(0.036 mole) were then added dropwise with stirring and cooling at atemperature below 25 C. Stirring was then continued for 2 further hoursat room temperature and the whole was allowed to stand overnight.Washing the-.mixture with dilute HCl, dilute bicarbonate, drying overmagnesium sulfate and high vacuum stripping gave 9 grams (87% yield) ofS-2,2,2-trichloroethyl- O ethyl methylthioprosphonate as yellowish oil,12 1.5644.

' EXAMPLE 21 10 grams (0.036 mole) of CP 16 were diluted with 75 ml. ofbenzene and 2.48 grams (0.04 mole) of ethyl mercaptan added atroomtemperature. 3.64 grams of triethylamine (0.036 mole) were thenadded slowly with stirring and cooling at a temperature not to exceed 25C. After the addition of the triethylamine, stirring was continued for afurther 2 hours and the mixture was allowed to stand overnight. Washingin order with dilute HCl, dilute bicarbonate, drying over magnesiumsulfate and high vacuum stripping gave 10.5 grams (97 percent yield) ofS-2,2,2-trichloroethyl-S-ethylmethylthiophosphonate as yellow oil, n1.6048.

EXAMPLE 22 10 grams (0.036 mole) of CP 16 were diluted with 100 ml. ofbenzene and 8.1 grams (0.08 mole) of diisopropylamine were added to themixture dropwise with stirring and cooling at a temperature between andC. Stirring for an additional 4 hours at room temperature (25 C.) andstanding overnight was applied followed by a 15 minute heating period to50 C. The cold mixture was then washed as usual with dilute HCl,bicarbonate and water, dried over anhydrous magnesium sulfate and vacuumstripped. 4.5 grams (87%5 yield) of S-2,2,2-trichloroethyl-methylphosphon N,N-di-isopropylamidate were obtained asdark amber oil, n 1.6044.

EXAMPLE 23 8 grams (0.033 mole) of CP 16 were diluted with 100 m1. ofbenzene, 2 grams (0.04 mole) of ethanol added at room temperature andreacted by dropwise addition of 3.5 grams of triethylamine (0.033 mole)with stirring and cooling at a temperature not to exceed C. Additionalstirring at room temperature for 1.5 hours, washing of the resultingmixture with dilute HCl, bicarbonate and water, drying over magnesiumsulfate and vacuum stripping gave -8 grams ofS-2,2-dichlorovinyl-S-ethyl-methylthiophosphonate as amber oil.

EXAMPLE 24 7 grams (0.029 mole) of CP 15 were dissolved in 100 ml. ofchloroform and 2.5 grams ethyl mercaptan excess together with 10 ml. ofchloroform added at room temperature. 3.39 grams (0.03 mole) oftriethylamine and 10 ml. of chloroform were added dropwise with stirringand occasional cooling at a temperature not to exceed 25 C. Washing withwater, dilute HCl, dilute bicarbonate, drying of the chloroform solutionover anhydrous magnesium sulfate and stripping in high vacuum gave 7.5grams (98% yield) of S-2,2-dichlorovinyl-S-ethylmethyl-thiophosphonateas almost colorless oil, n 1.6312.

EXAMPLE 25 8.0 grams of CP 15 (0.033 mole) were dissolved in 150 ml. ofbenzene and reacted by adding 7.51 grams (0.07 mole) ofdi-isopropylamine dropwise with stirring and cooling. Stirring for anadditional 1.5 hours at room temperature was applied to complete thereaction. After washing this solution with dilute HCl, dilutebicarbonate and water, drying over anhydrous magnesium sulfate and highvacuum stripping, 5 grams of S-2,2-dichlorovinyl methylthiophosphon-N,N-diisopropylamidate were obtained as reddish oil.

EXAMPLE 26 To 6 grams (0.0226 mole) of CP 22 in ml. of benzene therewere added at room temperature 1.4 grams (0.03 mole) of dry ethanol, 2.3grams (0.0226 mole) of triethylamine were then added with stirring andcooling dropwise at such a rate as to keep the temperature below 25 C.After completed addition, stirring for 1.5 hours at room temperature andstanding overnight, the mixture was washed in order with dilute HCl,dilute bicarbonate and water, dried over anhydrous magnesium sulfate andhigh vacuum stripped. 5 grams (78% yield) of S-2,2,2-trichloroethyl-O-ethyl-ethylphosphonate were obtained as yellow oil, n1.5085.

EXAMPLE 27 To 10 grams (0.036 mole) of CP' 22 in 75 ml. of benzene 2.5grams (0.04 mole) of ethyl mercaptan were added at room temperature. 3.6grams (0.036 mole) of triethylamine were then added dropwise withstirring and cooling at a temperature below 25 C. After completedaddition of the reagents stirring was continued for 2 /2 hours and thewhole was allowed to stand overnight. The mixture was washed as usualwith dilute HCl, dilute bicarbonate and water, dried over anhydrousmagnesium sulfate and high vacuum stripped. 10 grams (92% yield) ofS-2,2,2-trich1oroethyl-S-ethyl-ethylphosphonate were ob tained as yellowoil, 11 1.5565.

EXAMPLE 28 13.8 grams (0.05 mole) of CP 22 were dissolved in 150 ml. ofether and 10.1 grams di-isopropylamine (0.1 mole) were added slowlydropwise with stirring at room temperature. After completed addition ofthe reagent, stirring was continued at room temperature for oneadditional hour. The whole was washed with water, dried over magnesiumsulfate and high vacuum stripped. 1 gram ofS-2,2,2-trichloroethyl-ethylphosphon-N,N-di-isopropylamidate as aviscous oil was obtained. (Most of the compound was lost in the waterwash.)

EXAMPLE 29 To 10 grams (0.042 mole) of CP 23 dissolved in ml. ofbenzene, 2.3 grams (0.05 mole) of dry ethanol were added at roomtemperature. 4.22 grams (0.042 mole) of dry ethylamine were then addedslowly dropwise with stirring and occasional cooling at a temperaturenot to exceed 25 C. After completed addition of the reagent, stirringwas continued for 2 /2 hours and the whole was allowed to standovernight. :Washing of the resulting mixture as usual with dilute HCland dilute bicarbonate, drying over anhydrous magnesium sulfate andvacuum stripping gave 9 grams (87% yield) ofS-2,2-dichlorovinyl-O-ethyl-ethylphosphonate at red oil, n 1.5270.

EXAMPLE 30 10 grams (0.042 mole) of CP 23 were dissolved in 100 ml. ofpetroleum ether and 5 grams (slight excess over 2 molar proportion) in15 ml. of petroleum ether were added dropwise with stirring and coolingat a temperature below 10 C. (ice water bath). Stirring overnight,washing with water, dilute HCl, dilute bicarbonate, drying overmagnesium sulfate (50 cc. benzene were necessary to render mixturehomogeneous) and high vacuum stripping gave 9.5 grams (87 percent yield)S-2,2-dichlorovinyl-ethylphosphon-N-isopropylamidate as a light viscousoil, n 1.5460.

EXAMPLE 31 12 grams (0.05 mole) of CP 23 were dissolved in 100 ml. ofdry benzene and 11.1 grams (0.11 mole) of diisopropylamine were addedwith stirring dropwise at about 25 C. After completed addition of thereagents the mixture was stirred for 4 additional hours and finallyallowed to stand at room temperature overnight. Heating to 50 C. for 30minutes to complete the reaction and cooling followed by washing, dryingover anhydrous magnesium sulfate and high vacuum stripping, gave 1.5grams (10% yield) of S 2,2dichlorovinyl-ethyl-phosphon-N,N-di-isopropylamidate :as dark oil, n1.5500.

EXAMPLE 32 To 7 grams of CP 32 (0.24 mole) diluted with 75 ml. ofbenzene, 1.4 grams (0.3 mole) of dry ethyl alcohol were added at once atroom temperature. 2.5 grams (0.24 mole) of triethylamine diluted with 25ml. of dry benzene were then added dropwise with stirring and occasionalcooling at a temperature below 25 C. Standing overnight, washing of themixture with dilute HCl, dilute bicarbonate, drying over anhydrousmagnesium sulfate and high vacuum stripping gave grams (69% yield) ofS-2,2,2- trichloroethyl-O-ethyl-ethylphosphonate as a yellow oil, n1.5840.

EXAMPLE 33 grams (0.034 mole) of CP 32 were diluted with 75 ml. ofbenzene and 2.5 grams (0.04 mole) of ethyl mercaptan were added at roomtemperature. 3.5 grams (0.034 mole) of triethylamine diluted with ml. ofbenzene then were added dropwise with stirring and occasional cooling ata temperature below 25 C. Stirring for an additional 3 hours, allowingto stand overnight, washing the resulting solution in order with dryHCl, bicarbonate and water, drying over anhydrous magnesium sulfate andhigh vacuum stripping gave 10.5 grams (97% yield) of S 2,2,2triohloroethyl-S-ethyl-ethylthiophosphonate as a colorless oil, n1.5992.

EXAMPLE 34 14.6 grams (0.05 mole) of CP 32 were diluted with 150 ml. ofether and 10.1 grams of di-isopropylamine (0.1 mole) were added dropwisewith stirring and occasional cooling. The reaction is exothermic butprecipitation was poor. After completed addition, stirring was continuedfor one further hour. In order to complete the reaction (pH was stillbasic) the mixture was heated to slight reflux for minutes. Cooling,filtration with charcoal, and high vacuum stripping of the ethersolution without washing gave 9 grams ofS-2,2,2-trichloroethyl-ethylthiophosphon-N,N-di-isopropylamidate asviscous oil, 50% yield.

EXAMPLE 35 To a solution of 13 grams (0.02 mole) of CP 33 in 100 ml. ofbenzene 3 grams (0.06 mole) of dry ethyl alcohol were added followed by5 grams (0.05 mole) of triethylamine which was added slowly withstirring at room temperature. The addition temperature was kept below 35C. with occasional cooling. After completed addition, stirring wascontinued for two more hours at room temperature, cooled, washed asusual with dilute HCl, dilute bicarbonate and water, dried overanhydrous magnesium sulfate, filtered and high vacuum stripped. 10 grams(76% yield) of S 2,2-dichlorovinyl-O-ethyl-ethylthiophosphonate wereobtained as a yellow oil.

EXAMPLE 36 10 added at room temperature. 5 grams (0.05 mole) oftriethylamine were then added dropwise with stirring at room temperatureallowing the mixture to warm to 35 C. After completed addition, stirringwas continued for two more hours at room temperature, cooled, washed asusual with dilute HCl, dilute bicarbonate and water, dried overanhydrous magnesium sulfate, filtered and high vacuum stripped. 10 grams(76% yield) of S-2,2-dichlorovinyl-S-ethyl-thiophosphonate were obtainedas yellow oil.

EXAMPLE 37 To a solution of 12.8 grams (0.05 mole) of CP 33 in 100 ml.of benzene, 11.1 grams of di-isopropylamine (0.11 mole) were addeddropwise with stirring and cooling at 25 C. After completed addition ofthe reagent, stirring was continued for a further four hours. Allowingto stand overnight, heating to 50 C. for 30 minutes and coolingcompleted the reaction. The resulting mixture was then washed as usualwith dilute HCl, dilute bicarbonate and water, dried over magnesiumsulfate and high vacuum stripped. grams (60% yield, ofS-2,2-dichlorovinylethylthiophosphon N,N di-isopropylamidate wereobtained as amber oil, 11 1.5595.

EXAMPLE 38 9.72 grams (0.03 mole) of CP 8 were added dropwise withcooling to 60 ml. of dry ethyl alcohol-the large excess serving assolventfollowed by dropwise addition of 3 grams (0.03 mole) oftriethylamine with stirring and cooling at a temperature of below 35 C.After allowing the mixture to stir at room temperature for severalhours, the ethyl alcohol was evaporated in vacuum and the residue washedin water to remove most of the triethylamine hydrochloride. The formedoil was then taken up with Skellysolve B, washed twice with dilute HCland water, dried over magnesium sulfate and stripped in high vacuum. 10grams (quantitative yield) ofS-2,2,2-trichloroethyl-O-ethyl-phenylphosphonate was obtained as a lightyellow oil.

EXAMPLE 39 To a solution of 9.7 grams (0.03 mole) of CP 8 in 50 ml. ofdry benzene, 3.6 grams (0.06 mole) of mono-isopropylamine were addeddropwise with stirring at room temperature with occasional cooling.After completed addition of the reagent, the mixture was stirred for afurther two hours at room temperature. The resulting mixture was washed,dried over magnesium sulfate and high vacuum stripped. 9.5 grams (92%yield) of S-2,2,2-trichloroethyl-phenylphosphonmono-isopropylamidatewere obtained as a white solid, melting point 103-117 C.

EXAMPLE 40 9 .7 grams (0.03 mole) of CP 8 were diluted with 50 ml. ofbenzene and 6.1 grams (0.06 mole) of d'issopropylamine were addeddropwise with stirring at room temperature. Additional stirring for twohours and standing overnight completed the reaction. Washing as usual,drying over magnesium sulfate and high vacuum stripping gave 5 grams(43% yield) of S-2,2,2-trichloroethyl-phenylphosphon-diisopropylarnidate as yellow oil, 21 1.5445.

EXAMPLE 41 10 grams (0.035 mole) of CP 10 were dissolved in ml. ofbenzene and 2.12 grams (0.04 mole) of dry ethanol were added at roomtemperature. 4.04 grams (0.04 mole) of triethylamine were then addeddropwise with stirring and occasional cooling followed by an additionalstirring period of 2 /2 hours. Allowing to stand overnight, washing ofthe resulting mixture with dilute HCl, dilute bicarbonate and water,drying over anhydrous magnesium sulfate and high vacuum stripping gave10 grams of S-2,2- dichlorovinyl-O-ethyl-phenylphosphonate (97% yield)as red oil, n 1.5702.

EXAMPLE 43 14.3 grams (0.05 mole) of CP were diluted with 75 ml. ofbenzene and 6 grams (0.1 mole) of monoisopropylamine added with stirringat room temperature with occasional cooling. Standing overnight wasapplied for completion of the reaction. Washing of the obtained mixture,drying over magnesium sulfate and stripping in vacuum gave 12.5 grams(81% yield) of S-2,2-dichlorovinylphenylphosphon-monoisopropylamidate asa White solid, melting point 7587 C.

EXAMPLE 44 10 grams (0.035 mole) of CP 10 were diluted with 100 ml. ofbenzene at room temperature and 4.04 grams (0.04 mole) ofdi-isopropylamine were added dropwise with stirring at between -25 C.(cooling by means of an icewater bath). Additional stirring for 2 /2hours and standing overnight was applied to complete the reaction. Themixture was then Washed as usual, dried over magnesium sulfate and highvacuum stripped. 8.5 grams (70% yield) ofS-2,2,2-dichlorovinyl-phenylphosphon di isopropylamidate were obtainedas viscous oil, 11 1.5626.

EXAMPLE 45 10.2 grams (0.03 mole) of CP 9 were dissolved in 50 ml. ofbenzene and 3 grams (0.03 mole) of ethyl mercaptan were added at roomtemperature. To this mixture, 3 grams (0.03 mole) of triethylamine wereadded dropwise with stirring and occasional cooling at a temperature notto exceed C. After allowing to stir the mixture for an additional 2hours, washing of the resulting mixture as usual, drying over magnesiumsulfate and high vacuum stripping, 11 grams (quantitative yield)S-2,2,2- trichloroethyl S ethyl-phenylthiophosphonate were obtained ascolorless oil, n 1.6320.

EXAMPLE 46 10.2 grams (0.03 mole) of CP 9 were dissolved in 50 ml. ofbenzene and 3.6 grams (0.03 mole) of monoisopropylamine were addeddropwise with stirring and cooling at between 25 and C. Stirring wasthen continued for another two hours at room temperature and the wholewas allowed to stand overnight. The resulting mixture was washed asusual with dilute HCl, dilute bicarbonate and water, dried overanhydrous magnesium sulfate and high vacuum stripped. 9 grams (83%yield) of S-2,2,2-trichloroethylphenylthiophosphon-mono-isopropylamidate were obtained as a colorlessoil, 11 1.6666.

EXAMPLE 47 10.2 grams of CP 9 (0.03 mole) were diluted with 50 ml. ofdry benzene and 6.1 grams (0.06 mole) of di-isopropylamine were addeddropwise with stirring and cooling at room temperature. Allowing to stirfor a further two hours at room temperature and standing overnightcompleted the reaction. Washing with dilute HCl, dilute bicarbonate andwater of the resulting mixture, drying over magnesium sulfate and highvacuum stripping gave 7 grams (59% yield) ofS-2,2,Z-trichloroethyl-phenylthiophosphon-di-isopropylamidate as anoff-white solid, melting point 92100 C.

12 EXAMPLE 4s 10 grams (0.033 mole) of CP 11 dissolved in 100 ml. ofbenzene were mixed with 2.12 grams of dry ethanol (0.04 mole) of 4.04grams (0.04 mole) of triethylamine were added to this mixture dropwisewith stirring and occasional cooling at room temperature. Aftercompleted addition of the reagents, stirring was continued for a furthertwo hours at room temperature. After allowing the resulting mixture tostand overnight it was washed in succession with dilute HCl, dilutebicarbonate and water; drying over anhydrous magnesium sulfate and highvacuum stripping gave 10.5 grams (quantitative yield) of S-2,2-dichlorovinyl-0-ethyl-phenyl-thiophosphonate as a red oil, n 1.5900.

EXAMPLE 49 12 grams (0.039 mole) of CP 11 were dissolved in ml. ofbenzene and 4.7 grams (0.08 mole) of monoisopropylamine were addeddropwise with stirring and cooling at room temperature. After completedaddition of the reagent, the mixture was allowed to stand overnight.Washing, drying over magnesium sulfate and high vacuum stripping gave10.5 grams (81 percent yield) of S- 2,2dichlorovinyl-phenyl-thiophosphon-mono isopropylamidate as amber oil,11;, 1.6246.

EXAMPLE 50 10 grams (0.033 mole) of CP 11 diluted with 100 ml. ofbenzene and a mixture of 4.04 grams (0.04 mole) of di-isopropylamine and4.04 grams tri-ethylamine (0.04 mole) in 25 ml. of benzene is addeddropwise with stirring and cooling at 20--25 C. Additional stirring for2 hours and allowing to stand overnight gave after filtration, washing(dilute HCl, NaHCOg), drying (MgSO and high vacuum stripping 8 grams (66percent yield) of S- 2,2dichlorovinyl-phenyl-thiophosphon-di-isopropylamidate as a viscous oil,11 1.6400.

EXAMPLE 51 3.0 grams (0.62 M, excess) of methyl mercaptan gas wereintroduced at 70 C. into a solution of 8.7 grams (0.033 M) of CP 12 in60 ml. of dry Skellysolve B and 40 ml. of benzene. Then, with ice watercooling, 3.4 grams (0.033 M, slight excess) of Et N in 10 ml. of SkellyB were added dropwise with stirring at l5-20 C. After a two hourstanding period at room temperature, the mixture was washed (water,dilute HCl, dilute NaHCO dried (over MgSO and stripped in vacuum (.05mm. Hg, 50 C.), 7.5 grams (84 percent yield) ofS-2,2,2-trichloroethyl-S-methyl-methyl phosphonate were obtained asalmost colorless oil, which solidified on prolonged standing.

EXAMPLE 52 7.5 grams (0.0285 M) of CP 12 were dissolved in 70 ml. ofSkellysolve B, 4 grams (0.045 M, large excess) of -BuSH added withice-water cooling and 2.9 grams (0.0285 M) of Et N in 10 ml. ofSkellysolve B added at 1520 dropwise with stirring and cooling. Stirringfor a further 30' minutes at room temperature, washing (H dilute HCl,dilute NaHCO drying (MgSO and stripping (.05 mm. Hg, 70 C.) gave 7.5grams (85 percent yield) of S-2,2,2-trichloroethyl-S-butyl-methylphosphonate as pale yellow liquid.

EXAMPLE 53 7.6 grams (0.029 M) of CP 12 were dissolved in 50 ml. of 1:1Skellysolve B-Benzene and 6.2 grams (0.058 M) of N-methyl aniline in 20ml. of benzene added. The reaction proceeded at a reasonable rate atslightly elevated temperatures. When all the aniline was added a 2 hoursheating period at 55 C. was sufiicient to complete the reaction. Coolingto room temperature and filtration,

13 followed by washing (dilute HCl, NaHCO and water), drying (MgSO andvacuum stripping gave 8 grams ('85 percent yield) of S-2,2,2-trichloroethyl-methyl-phosphon-N,N-methyl-phenyl amidate as a light brown oilwhich solidified on prolonged standing.

EXAMPLE 54' 2.2 grams (0.025 M) of piperazine and 5.1 grams (0.05 M) of'Et N were dissolved together in 100 ml. of CHCl 13.8 grams (0.5 M) ofCP 22 (S-2,2,2-trichloroethylethyl thiophosphonyl chloride) were thenslowly added dropwise with stirring at 20-25 C. and occasional cooling.Two hours continuous stirring at room temperature, washing (water,dilute HCl, dilute HCl, dilute NaHCO drying (MgSO and stripping gave11.5 g. (80%) of bis[S 2,2,2 trichloroethyl-ethyl-thiophosphonyl]piperazine-l,4 as crude dark oil, which solidified. Washing with freshbenzene gave a bulf colored solid, M.P. 1608 C., percent Cl 37.7 calc.,36.5 fd. percent P 11.0 calc., 10.9 fd.

EXAMPLE 55 8 grams (0.025 M) of CP 8 were dissolved in 150 ml. of drypetroleum ether and a total of 3 grams (0.067 M, excess) of dimethylamine gas was introduced at a temperature below 10 C. with stirring andcooling over a period of approximately minutes. Prolonged stirringEXAMPLE 56 9.72 grams (0.03 M) CP 8 were dissolved in 75 ml. petroleumether and 25 ml. of benzene, 4.24 grams (0.029 M) of p-chloro thiophenoladded at room temperature followed by dropwise addition with stirringand cooling of 3 grams (0.03 M) of Et N at below 35 C. followed in turnby heating for 30 minutes at 55 C. and allowing to cooltto roomtemperature with stirring. Washing (water, dilute HCl, dilute NaHCOdrying over anh. MgSO and stripping in high vacuum gave 11.5 grams (89percent yield) ofS-2,2,Z-trichloroethyl-S-p-chlorophenyl-phenyl-phosphonate as a veryheavy oil, n 1.6415; percent Cl 32.9 cal., 33.2 fd., percent P 7.2 cal.,6.8 fd.

EXAMPLE 57 9.72 grams (0.03 M) of CP 8 were dissolved in a mixture of 75ml. petroleum ether and 25 ml. benzene, 3.8 grams (0.03 M) ofp-chlorophenol added followed by dropwise addition with stirring andcooling at below 35 C. of 3 grams (0.03 M) of Et N. A short period ofheating to 55 C. and allowing to cool to room temperature over a totalperiod of 1 hour was applied to assure quantitative reaction. Washing(water, dilute HCl, dilute NaCHO drying (MgSO and stripping (vacuumygave11.0 grams (88 percent yield) of S-2,2,2-trichloroethyl-O-p-chlorophenyl-phenyl-phosphonate, percent CI 34.2 cal.. 33 id, percentP 7.5 fd.

EXAMPLE 58 14 which on recrystallizing gave 111. 93-6 C. percent CI 24.9cal., 24.9 fd., percent P 7.3 cal., 7.5 fd., percent N 3.3 cal., 3.2fd.; (IR 57).

The pesticides of the present invention can be used alone or they can beapplied together with inert solids to form dusts, or can be suspended ina suitable liquid dilute, e.g., organic solvents or water.

There can also be added surface active agents or wetting agents and/orinert solids in the liquid formulations. In such case, the activeingredient can be from 0.01 to 95% by weight of the entire composition.

As organic solvents there can be employed hydrocarbons, e.g. benzene,toluene, xylene, kerosene, diesel fuel, fuel oil, and petroleum naphtha,ketones such as acetone, methyl ethyl ketone and cyclohexanone,chlorinated hydrocarbons such as carbon tetrachloride, chloroform,trichloroethylene, and perchloroethylene, esters such as ethyl acetate,amyl acetate and butyl acetate, ethers, e.g. ethylene -glycol monomethylether and diethylene glycol monomethyl ether, alcohols, e.g. methanol,ethanol, isopropan01, amyl alcohol, ethylene glycol, propylene glycol,butyl carbitol acetate and glycerine. Mixtures of water and organicsolvents, either as solutions or emulsions, can be employed.

The novel pesticides can also be applied as aerosols, e.g. by dispersingthem in air by means of a compressed gas such as dichlorodifluoromethaneor trichlorofluoromethane and other Freons and Genetrons, for example.

The pesticides of the present invention can also be applied withadjuvants or carriers such as talc, pyrophyllite, synthetic fine silica,attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calciumcarbonate, bentonite, fullers earth, cotton-seed hulls, wheat flour,soybean flour, pumice, tripoli, wood flour, walnut shell flour, redwoodflour and lignin.

As stated, it is frequently desirable to incorporate a surface activeagent in the pesticidal compositions of the present invention. Suchsurface active or wetting agents are advantageously employed in both thesolid and liquid compositions. The surface active agent can be anionic,cationic or nonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acidesters of polyhydric alcohols and the alkylene oxide addition productsof such esters, and addition products of long chain mercaptans andalkylene oxides. Typical examples of such surface active agents includethe sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in thealkyl group, alkylphenol ethylene oxide condensation products, e.g.p-isooctylphenol condensed with 10 ethylene oxide units, soaps, e.g.sodium stearate and potassium oleate, sodium salt of propylnaphthalenesulfonic acid, di (Z-ethylhexyl) ester of sodium sulfosuccinic acid,sodium lauryl sulfate, sodium decane sulfonate, sodium salt of thesulfonated monoglyceride of cocoanut fatty acids, sorbitan sesquioleate,lauryl trimethyl ammonium chloride, octadecyl trimethyl ammoniumchloride, polyethylene glycol lauryl ether,

polyethylene glycol esters of fatty acids and rosin acids,

e.g. Ethofat 7 and 13, sodium N-methyl-N-oleyl taurate, Turkey Red Oil,sodium dibutyl naphthalene sulfonate, sodium lignin sulfonate,polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiarydodecyl polyethylene glycol thioether (Nonionic 218), long chainethylene oxide-propylene oxide condensation products, e.g. Pluronic 61(molecular weight 1000), polyethylene glycol ester of tall oil acids,sodium octyl phenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitanmonostearate (Tween 60), and sodium dihexyl sulfosuccinate.

The solid and liquid formulations can be prepared by any of theconventional procedures. The compounds of the present invention can beapplied to soil, growing plants, e.g. trees, cotton plants, wheat andother grain plants, vegetable plants, seeds, fabrics, etc. to givepesticidal protection.

TABLE 2.AGAR PLATES Soil fungicide rolled towel, #IA Pythium Spore germ.

Example Structure, Me. 200 50 500 100 10 Et OEt 0 0 SE; 2 2 CC1 =CHS-PNHiPro 2 0 NiPro: 7 3

El; S OEt 0 0 81% 0 0 CC13CHzS-P NHiPro 5 NiPXO 0 0 Et S OEt 5 4 SE: 3 5C C1:=CHSP NHiPro 0 0 0 0 0 NiPro 7- s Structure, P11

Ph 0 OEt 0 0 0 0 0 SEt 7 0 0 0 0 CClaCHnS P NHiPro l 0 0 0 0 NiPro; 0 05 0 0 Ph 0 CE: 3 2 0 0 0 SE1; 0 0 5 0 0 C C12=CH S P NHiPro 2 2 0 0NiPIOz 5 0 Ph S 0131; 0 0 10 5 0 SE; 0 0 0 0 0 O ClsCHzS P NHlPro 0 0 00 0 NiPro 0 0 0 0 0 Ph S OEt 2 3 SE1; 0 0 5 0 0 CCl =CHSP NHiPro 4 4 0 00 NiPlOz 1 0 Structure, additional compounds 51 CC1aCH2S(CHa)P(O)SCH:

53 OC1sCH2S(CH3)P(O)-SCH1N(CH3) COI'IE [00130111 s 0211;) P( )h N HOMOThe compounds were also tested as nematocides against both saprophyticand parasitic nematodes at the rates of test compound in parts permillion (ppm) set forth in Table 3. In the saprophytic nematode test(NESA) water was used as the medium with Panagrellus spp. and Rhabditisspp. The formulation employed included of the compound being tested, 46%silica, 2% sodium lignin sulfonate and 2% Pluronic L-6l (polyethyleneoxide, propylene oxide adduct molecular weight about 1000). Thisformulation is Formulation A. The results are given on a 0 to 10 scalewith 10 indicating kill and 0 indicating no kill after a 4-dayincubation period.

In the parasitic nematode test (NI-EPA) the procedure was to add thetest chemical in Formulation A to soil heavily infested with Meloidogynespp. Then tomato plants were transplanted into the soil and allowed togrow. The root knots which formed on the roots of the plant were thenmeasured according to a root knot index based on a 0-10 scale where 10indicates complete absence of visible knotting and 0 indicates all rootswere heavily infested (knotted). Tomato plants transplanted to theinfested soil which did not contain the nematocide had an average rootknot index of 0 while tomato plants transplanted to soil which had beensteamed to kill all nematodes had an average root knot index of 10. Theterm Ph in Table 3 indicates phytotoxicity. As can be seen from Table 3some of the compounds most effective against saprophytic nematodes had aconsiderably lesser effect against parasitic nematodes and vice versa.This is in accordance with the known fact that nematocide activity isnot predictable.

TABLE 3 NE SA NEPA Example Structure, Me 400 200 0 Et l0 8 SE1; 10 10 NHiPro 8 5 NiPrOz 1 1 OEi; 5 0 SE1; 10 1O NHiPro 1O 10 NiPrOz 10 10 OEt 50 SEt 0 0 NHiPro 5 3 NiPro 1 1 The compounds were also tested asdefoliants and desiccants at the indicated dosages in lbs/acre. Theresults are set forth in Table 5. The compounds in acetone solution weresprayed on cotton plants in the squaring stage of development.Defoliation was determined after 7 days and is based on a 0-10 scalewhere 0 is no effect and 10 indicates 100% defoliation. Desiccation isalso after 7 days and is based on a 0-10 scale where 0 indicates noeffect and 10 indicates complete desiccation.

Regrowth also measured on Table 5 was determined 5 days after thedefoliation data was recorded and is also on a 0 to 10 scale where O isno control and 10 is completed control of regrowth. The compounds of thepresent invention had only slight defoliation and desiccation propertiesand no control of regrowth. This of course is desirable in pesticidesapplied to growing crops.

TABLE 5.-AT NUMBER 1A.

Defoliant-desiccant Defoliant Desteeant Regrowth Example Structure, Me 84 2 1 8 4 2 1 8 4 2 1 Me 0 OEt 0 0 1 1 0 0 SEt 2 0 3 3 0 0 0 CO13CH2SPNHiPro 0 0 6 3 0 0 NiPro:

Me 0 0E1: 0 0 0 7 5 4 0 0 0 SEt 3 4 0 1 0 0 0 CCI2=CHS-P NHiPro NiPro:2st

C C15CH2SP NHiPro NiProa Me S OEt 0 0 0 4 2 1 0 0 SE1; G Ch=CHS-P NHiPro0 0 0 3 2 1 0 0 0 NiPro:

Structure, Et

Et 0 OEt SEt 0 0 0 4 3 2 0 0 0 001 0111 S-P NHiPro 0 0 0 3 3 1 0 0 0NlPlOz Et 0 0E1; 0 4 3 1% 3 a 4 OCh=CHS-P NHiPro O 2 2 NiProa Et S OEtSEt 0 2 2 0 0 0 CClaCHaS-P NHiPro 0 2 1 0 0 0 NiProa 0 4 3 0 0 0 E1; SOEt 0 3 3 0 0 0 SEt 0 2 1 0 0 0 CG1z=CHS-P NHiPro 0 3 1 0 0 0 NiPrOz 0 41 0 0 0 Structure, Ph

Ph 0 OEt 0 2 r SEt 0 1 CClaUHzS P NHiPro 0 0 1 NiProz Ph 0 OEt 0 0 3 2 20 0 0 SEt 0 0 4 4 3 2 0 0 C Ch=CH S P NHiPro 0 0 3 3 1 0 0 0 NiPro; 0 02 1 1 0 0 0 Ph 8 OEt 0 0 2 1 2 0 0 0 SEt 0 0 1 1 1 0 0 0 CClaCHzS PNHiPro 0 0 2 2 1 0 0 0 NiPron 0 0 l 1 1 0 0 0 Ph S OEt 0 0 2 2 2 0 0 0SEt 0 0 2 1 1 0 0 0 001 :0118 P NHiPro 0 0 1 1 1 0 0 0 NiPro; 0 0 4 2 20 0 0 Structure, additional compounds CC13CH2S(CH3)P(O)-S CH 0 4CClaCHzS(CH )P(O)--S(CH2)aCHa 0 6 CC1 CH2S(CH )P(O)-O (240190511 0 2 53CCIsCHzS (CH3) P(O)N(CHs)CeHa 0 1 Additionally the compounds were testedas insecticides The compounds having a P=S linkage on the whole as shownin Table 6. In the table the rates are in mmg. appear to be betterpesticides than the compounds having (micrograms)/dish. The results areindicated after 2 Q a P linkage. hours and 18 hours for the flour beetleand the housefiy. In the tests reported in the tables, the most usefulcom- A number of the compounds were very effective as is pounds were2,2-dichlorovinyl-S-ethyl methyl thiophosindicated by the results on thescale where 0 is no kill phonate (nematocide and to a lesser extent soilfungicide); and 10 is 100% kill. S-2,2,2-trichloroethyl ethyl phosphonmonoisopropyl ami- TABLE 6.INSECTICIDES [Rates at 111mg. dish] Flourbeetles House fly 2 hrs. 18 hrs. 2 hrs. 18 hrs.

Example Structure, Me 1,000 100 10 1,000 100 10 1,000 100 10 1,000 10010 Me\ /O glljitt t OClzCEhS-P NHiPro NiPIOz Me 0 01% SEt OOI2=CHS PNHiPro NiPI'Og Me\ S CClaOH;S-P NHiPro NiPIO:

Me S OEt SE1; 0 Ol2=GHS-P NHiPro NiPlOz Structure, Et Big 0 (slgt t COlaOHzS-P NHiPro NiPro SEt OOl2:CHS-P NHiPro NiPlDz a t C 01; OHzS-PNHiPro NiPXOz Et\ S gfit t CCl2=CHS-P NHiPro NiPr02 Structure, Ph

013?; 70 0 0 100 80 0 0 0 0 80 0 0 SEt 0 00 37 0 0 0 0 0 0 0 0 NHiPro 00 0 0 0 0 10 1G 23 13 NiProz 0 0 0 0 0 0 6 3 0 50 30 t 4 NHiPro 0 0 0 00 0 0 0 0 36 30 13 Nilro 0 0 0 6 0 0 0 0 0 10 6 3 OEt 6 0 0 83 0 0 0 0 0100 96 50 SE1; 0 0 0 66 6 0 0 0 0 26 20 NHiPro 3 3 0 16 6 0 0 0 0 100 4630 NiProz 0 0 0 0 0 0 0 0 0 30 16 13 OEt 3 0 0 33 3 0 3 6 0 100 16 13SEt 0 0 0 63 0 0 3 0 0 46 10 3 NHiPro 0 0 0 0 0 0 0 0 0 36 26 10 NiPlOz0 0 0 13 0 0 3 3 0 13 10 13 Structure, additional compoundsCCl3CHzS(CHs)P(O)-SCH: 100 0 0 100 0 0 100 30 0 100 75 10CCIQCHzS(CH3)P(O)-S(CI'I2)3CH3 75 15 0 100 100 0 100 5 0 100 5 0CC13CH2S(CH3)P(0)O(2,4C12)C6H3 6 3 0 100 100 0 0 0 0 0 0 0 53CClaCHzS(CH3)P(O)N(CH3)C6H5 0 0 0 0 0 0 0 0 0 0 0 54[CC13CH2S(C:H5)P(S)]2 N N 55 001301125(C@I 5)P(O)N(OHs)z 30 0 0 0 0 0 00 25 10 0 OC13CH2S(CaH )1(O)-S(4CDCH4 0 0 0 35 0 0 0 0 0 5 0 0CClaCHzS(C H )P(O)O(4Cl)CsH4 50 0 0 50 0 0 0 0 0 0 0 0.001301128(CBHE)P(O) O(4N i) G J 0 0 0 0 0 0 0 0 0 0 0 0 9..CC1z=CHS(CoH5)P(O)-N(CH3)2 0 0 0 10 0 0 0 0 0 5 0 The generalobservations from the tests are that the date (soil fungicide and to alesser extent saprophytic areas of activity of the series of compoundstested ap- 70 nematocide); S-2,2,2-trichloroethyl-O-ethyl methylthiopears to be in the order nematocidal, insecticidal and phosphonate(namatocide); S-2,2,2-trichloroethyl-S-ethyl fungicidal in the givenorder of priority. methyl thiophosphonate (nematocide);S-2,2,2trichloro- The compounds Where R is lower alkyl, e.g. methyl orethyl-S-ethyl ethyl thiophosphonate (nematocide); S-2,2, ethyl appear tobe superior pesticides to those where R 2-trichloroethyl methylthiophosphon monoisopropyl amiis phenyl. date (insecticide);S-2,2,2-trichloroethyl ethyl thiophosphon monoisopropyl amidate(insecticide and to a lesser extent saprophytic nematocide);S-2,2,2-dichlorovinylethyl thiophosphon monoisopropyl amidate(insecticide and to a lesser extent parasitic nematocide and platefungicide); and S-2,2,2-dichlorovinyl ethyl thiophosphon monoisopropylamidate (soil fungicide).

What is claimed is:

1. A method of killing nematodes comprising applying to the nematodes anematocidally efiective amount of a compound having the formula where Ris trichloroethyl or dichlorovinyl, R is lower alkyl or phenyl, R iswhere R is lower alkyl, phenyl, naphthyl, tolyl, chlorophenyl orbromophenyl; R is hydrogen or R and X is O or S.

2. A process according to claim 1 wherein R is 2,2,2- trichloroethyl.

3. A process according to claim 1 wherein R is 2,2- dichlorovinyl.

4. A process according to claim 1 wherein R is lower alkyl and R ishydrogen or lower alkyl.

5. A process according to claim 4 wherein R is hydrogen.

6. A process according to claim 4 wherein X is O.

7. A process according to claim 4 wherein X is S.

8. A method of killing insects comprising applying to the insects aninsecticidally effective amount of a compound having the formula 30where R is trichloroethyl or dichlorovinyl, R is lower alkyl or phenyl,R is where R is trichloroethyl or dichlorovinyl, R is lower alkyl orphenyl, R is where R is lower alkyl, phenyl, naphthyl, tolyl,chlorophenyl or bromophenyl; R is hydrogen or R and X is O or S.

References Cited UNITED STATES PATENTS 3,093,536 6/1963 Loefier 260-957X JEROME D. GOLDBERG, Primary Examiner A. J. ROBINSON, AssistantExaminer US. Cl. X.R. 424219, 222

